Filler and transparent resin composition, and method for producing same

Abstract

To provide a transparent resin material having mechanical characteristics, and optical characteristics different from those of conventional one.SOLUTION: A filler has a transparent resin material comprising a two liquid type silicone as a main constituent, and a particle material used by dispersing in the transparent resin material. The particle material has a specific surface diameter of 0.8 nm or more and 80 nm or less, and is an aggregate of a primary particle an inner part of which is constituted by at least one of boehmite and γ-alumina, and a surface of which is constituted by silica. The volume average particle size thereof is larger than 0.1 μm. The particle material is formed such that the refractive index is 1.50-1.60 by surface treating with a surface treating agent having a double bond, and has a modified layer for coating the surface of the primary particle, where the modified layer binds to the surface of the primary particle by covalent bond or intermolecular bond.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a transparent resin composition for electronic devices such as LED devices and a method for producing the same, and more particularly to a filler to be filled in a transparent resin composition, the transparent resin composition, a method for producing the same, and an LED device using the transparent resin composition. [Background technology]

[0002] Conventionally, transparent resin compositions for electronic components such as LED encapsulants are required to have sufficient transparency, mechanical properties, and electrical properties over a long period of time, and alicyclic epoxy resins and silicone resins have been used for this purpose. Silicone resins, in particular, are widely used in transparent resin compositions because of their excellent yellowing resistance. Transparent resin compositions in which particulate material made of inorganic material is dispersed have been produced as transparent resin materials (Patent Documents 1 to 4). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2009-221350 A [Patent Document 2] JP 2006-219356 A [Patent Document 3] JP 2007-154159 A [Patent Document 4] JP 2011-251906 A Summary of the Invention [Problem to be solved by the invention]

[0004] Here, the transparent resin composition is required to have high hardness because scratches have a significant effect on transparency, and since silicone resin has high gas permeability, sulfur dioxide gas, sulfur gas, etc. may penetrate and affect the sealed electronic device, so it is required to have low gas permeability.

[0005] The present invention was completed in consideration of the current situation, and an object of the present invention is to provide a transparent resin composition having mechanical properties and optical properties different from conventional ones, a filler suitable for filling the transparent resin composition, a manufacturing method thereof, and an LED device utilizing the transparent resin composition. [Means for solving the problem]

[0006] In order to solve the above problems, the present inventors have conducted extensive research and found that by forming an aggregate of primary particles having a certain particle size, when used as a filler, it is possible to improve the mechanical properties while maintaining the optical properties compared to when the particle size is simply increased, and further, by configuring the primary particles so that the composition of the inorganic material differs between the inside and the surface, and by surface-treating the primary particles with a surface-treating agent having a double bond, it is possible to incorporate inorganic materials that have been difficult to use mainly for reasons other than optical properties.By introducing a surface-treating agent having a double bond to the surface so that the refractive index becomes 1.50 to 1.60 by surface treatment, it is possible to form a strong bond with silicone and obtain a transparent resin composition with high transparency.

[0007] The primary particles that make up the aggregates have an internal composition of gamma alumina or boehmite, and a structure with silica on the surface. Because the surface composition and internal composition are set independently, it has been found that it is easier to control the optical properties obtained, unlike inorganic materials that mix the two at the atomic level. Furthermore, the strength of the particles is improved by forming aggregates in which the particles are bonded and fused together by dehydration condensation.

[0008] Since the primary particles are bonded and fused together, the particle size of the primary particles is not directly specified, but is specified by the specific surface area diameter based on the surface that is connected to the outside. In other words, when forming a composition, the transparent resin material that forms the matrix can fill the gaps between the primary particles. Therefore, the size of the primary particles has a large effect on the optical properties.

[0009] That is, the filler of the present invention which solves the above problems is a filler having a particulate material which is dispersed in a transparent resin material mainly composed of a two-component silicone, The particulate material comprises: The specific surface area diameter based on the surface that is connected to the outside is 0.8 nm to 80 nm, and the primary particles are made of inorganic matter whose surface composition and internal composition are different. It is an aggregate in which particles are bonded and fused together by dehydration condensation, The volume average particle size of the aggregates is greater than 0.1 μm; the surface composition has a refractive index different from that of the interior composition; the abundance ratio of the surface composition to the internal composition is such that a transmittance (wavelength 400 nm) of a cured product having a thickness of 2 mm obtained by dispersing and curing 10 parts by mass of the aggregate in 100 parts by mass of the transparent resin material is 80% or more; the primary particles each have an interior composed of at least one of boehmite and γ-alumina and a surface composed of silica; The primary particles are surface-treated with a surface treatment agent having a double bond so that the refractive index is 1.50 to 1.60, and the primary particles have a modified layer made of an organic substance that coats the surfaces of the primary particles; The modified layer is bonded to the surface of the primary particles by covalent bonding or by intermolecular forces.

[0010] The particulate material preferably has a volume average particle size of 0.2 μm to 5.0 μm. The surface treatment agent is a silane compound, and has a volume average particle size of 2.0 to 6.8 μmol / m based on the surface of the aggregate that communicates with the outside. 2 It is preferable that the surface treatment agent has one or more double bond-containing functional groups selected from a vinyl group, a methacryl group, and an acryl group.

[0011] The particulate material preferably has a modified layer made of an organic material that covers the surface of the primary particles, and the modified layer is preferably bonded to the surface of the primary particles by covalent bonding or intermolecular bonding. The organic material is preferably a condensation product of a silane compound. In particular, the electronic device is preferably an LED.

[0012] A method for producing a transparent resin composition that solves the above problems is a method for producing a transparent resin composition of the present invention, comprising the steps of: a dispersing step of dispersing core particles having the internal composition in a liquid dispersion medium to obtain a dispersion; a coating step of dissolving a precursor of the surface composition in the dispersion liquid, and then converting the precursor into the surface composition to coat the core particles to form coated particles; an aggregation step of heating the coated particles to cause dehydration and condensation to bond and fuse the particles together to form aggregates; a modification step of forming a modified layer made of an organic substance that coats the surface of the coated particle by surface-treating the surface of the coated particle with a surface treatment agent having a double bond so that the refractive index is 1.50 to 1.60, and the modified layer is bonded to the surface of the coated particle by covalent bonding or intermolecular bonding; a mixing step of mixing the particulate material obtained by the aggregation step and the modification step with the transparent resin material to form a transparent resin composition; has.

[0013] The surface treatment agent is a silane compound, and has a concentration of 2.0 to 6.8 μmol / m based on the surface of the aggregate that communicates with the outside. 2 It is preferable that the surface treatment agent has one or more double bond-containing functional groups selected from a vinyl group, a methacryl group, and an acryl group.

[0014] The LED device of the present invention which solves the above-mentioned problems comprises the transparent resin composition of the present invention and an LED chip encapsulated with the transparent resin composition. Effect of the Invention

[0015] By dispersing a particulate material that has been surface-treated with a surface treatment agent having a double bond and has a different surface composition from its internal composition in a transparent resin material mainly composed of a two-component silicone, a strong bond is formed between the transparent resin material and the particulate material, and transparency can be maintained. The particulate material used here can be suitably used as a filler. [Brief description of the drawings]

[0016] [Figure 1] 1 is a graph showing the indentation hardness of each sample in the examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The filler and transparent resin composition of the present invention, as well as the production method thereof, and the LED device will be described in detail below with reference to the embodiments.

[0018] (Transparent resin composition and filler) The transparent resin composition of the present embodiment is used in electronic devices. Examples of electronic devices that can be used include light-emitting devices such as LED devices and organic EL devices, and light-receiving devices such as phototransistors. It is preferable that the transparent resin composition seals the light-emitting chip or light-receiving chip of the light-emitting device and forms an optical path for passing light. The transparent resin composition of the present embodiment has high transparency, low coefficient of thermal expansion (CTE), high gas barrier properties, high elastic modulus, high surface hardness, high compressive strength, and high anti-blocking properties.

[0019] The transparent resin composition of the present embodiment has a particulate material as a filler, a transparent resin material for dispersing the particulate material, and other materials that are contained as necessary. The filler of the present embodiment may use the particulate material alone, or may contain other particulate materials. The ratio of other particulate materials in the filler may be up to 30%, 20%, 10%, 2%, or 0% based on the mass of the entire filler.

[0020] Other particulate materials that can be contained are required to have a certain degree of transparency to visible light, so it is preferable that they have a particle size sufficiently smaller than the wavelength of the light for which transparency is required. For example, the upper limit of the particle size of other particulate materials can be 300 nm, 200 nm, 150 nm, 100 nm, 80 nm, 50 nm, 30 nm, or 10 nm. Other particulate materials can be composed of silica, alumina, zirconia, titania, or composite oxides thereof, and can also be surface-treated. Examples of surface treatments include substances that bond to the surface (such as silane compounds) and substances that adhere to the surface (such as organic substances such as acidic substances and alkaline substances).

[0021] The transparent resin composition of the present embodiment may be in a solid or liquid state. When it is in a liquid state, it is preferable to cure it to a solid state while it is in a state where it is used in an electronic device to which it is to be applied.

[0022] The transparent resin composition of this embodiment has a light transmittance of 80% or more, and preferably 85% or more, or 90% or more. The light transmittance is measured using a test sample having a thickness of 2 mm and a light beam having a wavelength of 400 nm. The mixing ratio of the filler and the transparent resin material is determined within a range in which the above-mentioned light transmittance can be achieved. In terms of improving mechanical properties, it is preferable to have a high ratio of filler. The mixing ratio of the filler and the transparent resin material is not particularly limited, but any combination of a lower limit of 1%, 3%, or 5% and an upper limit of about 15%, 25%, or 35% of the filler based on the mass of the entire transparent resin composition can be used.

[0023] ·Transparent resin material The transparent resin material is mainly composed of two-component silicone. "Mainly composed of two-component silicone" means that the transparent resin material contains 50% or more of two-component silicone based on its mass. The lower limit of the content of two-component silicone can be 60%, 70%, 80%, 90%, or 100%. Two-component silicone is a material that is polymerized and solidified by mixing and reacting two types of silicone precursors with different chemical formulas. It may also contain a curing catalyst at the same time. In the transparent resin composition of this embodiment, the two-component silicone may be in the form of a precursor before the reaction or in the form after the reaction and curing. The two-component silicone may contain other additives.

[0024] Two-component silicone is a material that produces polymeric silicone by addition polymerization, and is made by mixing and curing a vinyl-containing organopolysiloxane (agent A) having a siloxane unit with a vinyl group and an organohydrogenpolysiloxane (agent B) having a siloxane unit with a SiH group. The mixing ratio of agent A and agent B is not particularly limited, but they are usually mixed in a stoichiometric ratio. Since the presence of a modified layer formed by a surface treatment agent having a double bond affects the polymerization reaction of the two-component silicone, it is preferable to change the mixing ratio of agent A and agent B. The transparent resin material may be a cured product of the two-component silicone, or may be in a state before curing.

[0025] Examples of the siloxane units of the vinyl group-containing organopolysiloxane constituting the A agent include monovinylsiloxane, monomethylsiloxane, monoethylsiloxane, monophenylsiloxane, divinylsiloxane, phenylvinylsiloxane, methylphenylsiloxane, diphenylsiloxane, dimethylsiloxane, trivinylsiloxane, divinylmethylsiloxane, divinylphenylsiloxane, vinyldimethylsiloxane, vinylphenylmethylsiloxane, trimethylsiloxane, dimethylphenylsiloxane, methyldiphenylsiloxane, triphenylsiloxane, and further siloxanes in which the hydrogen atoms of the organic groups of these siloxanes are substituted with halogens, etc. The vinyl group-containing organopolysiloxane constituting the A agent can be obtained by co-hydrolysis and condensation of a mixture of two or more halosilanes and / or alkoxysilanes corresponding to these siloxane units.

[0026] The organohydrogenpolysiloxanes that make up Agent B include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(dimethylhydrogensiloxy)methylsilane, tris(dimethylhydrogensiloxy)phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, methylhydrogenpolysiloxane blocked at both ends with trimethylsiloxy groups, and methylhydrogenpolysiloxane blocked at both ends with trimethylsiloxy groups. Silyl-terminated dimethylsiloxane-methylhydrogensiloxane copolymer, dimethylpolysiloxane terminated with dimethylhydrogensiloxy groups at both ends, dimethylsiloxane-methylhydrogensiloxane copolymer terminated with dimethylhydrogensiloxy groups at both ends, methylhydrogensiloxane-diphenylsiloxane copolymer terminated with trimethylsiloxy groups at both ends, methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymer terminated with trimethylsiloxy groups at both ends, (CH3)2HSiO 1 / 2 Units and SiO 4 / 2 A copolymer consisting of (CH3)2HSiO units. 1 / 2 Units and SiO 4 / 2 Units and (C6H5)3SiO 3 / 2 and copolymers in which some or all of the methyl groups in these exemplary compounds have been replaced with other alkyl groups such as ethyl groups and propyl groups, or halogen-substituted alkyl groups such as 3,3,3-trifluoropropyl groups.

[0027] Particulate material contained in filler The particulate material has an aggregate and a modified layer formed on the surface of the aggregate. The aggregate is formed by the primary particles bonding and fusing together through dehydration condensation. The modified layer is formed by surface treatment with a surface treatment agent that has double bonds.

[0028] The refractive index of the particle material is 1.50 to 1.60. The refractive index is controlled by changing the type and amount of the surface treatment agent to control the refractive index of the modified layer. By adopting a surface treatment agent having a higher refractive index than the aggregates, the refractive index of the particle material can be made higher than that of the aggregates, and conversely, by adopting a surface treatment agent having a lower refractive index than the aggregates, the refractive index of the particle material can be made lower than that of the aggregates. In addition, by increasing the amount of the surface treatment agent, it is possible to bring the refractive index closer to the value of the surface treatment agent.

[0029] The refractive index of the particle material is measured by the following method. Prepare multiple levels of mixed solvents with different blend ratios of two types of solvents with known refractive indices, and disperse the particle material in these at a concentration of 100 g / L. The refractive index of the mixed liquid at the point where the transmittance is 80% or more (589 nm / 10 mm) and the mixed liquid is the most transparent is taken as the refractive index of the particle material.

[0030] The aggregates that make up the particulate material are bonded and fused between primary particles, so the primary particles are firmly bonded together, improving the mechanical strength of the particulate material. Since the strength can be improved as the particle size increases, it is preferable to increase the particle size as much as possible while still allowing mixing, and the volume average particle size is greater than 0.1 μm. For example, when the particulate material is applied to a form that may not be physically penetrable, such as a thin film, the appropriate particle size distribution of the particulate material is determined so that it can physically penetrate the form of the part to which it is applied.

[0031] Preferable lower limits of the volume average particle diameter are 0.2 μm, 0.5 μm, 1.0 μm, etc. Preferable upper limits of the volume average particle diameter are 5.0 μm, 4.0 μm, 3.0 μm, 2.0 μm, etc. Furthermore, it is possible to have multiple particle diameter peaks, such as large and small particle diameters.

[0032] The particulate material contained in the filler of this embodiment has a specific surface area diameter of 0.8 nm to 80 nm based on the surface that communicates with the outside air. The specific surface area diameter is a value calculated from the specific surface area (surface area per unit mass) and the specific gravity of the material that constitutes the particulate material, and for secondary particles that are formed as aggregates of primary particles, a value close to the particle size of the primary particles that constitute the secondary particles is calculated.

[0033] The specific surface area diameter can adopt lower limits of 1 nm, 5 nm, and 10 nm, and upper limits of 30 nm, 50 nm, and 70 nm.

[0034] The primary particles constituting the aggregate (hereinafter, appropriately referred to as "constituent primary particles") are made of inorganic materials with different surface and internal compositions. By making the surface and internal compositions different, the material constituting the interior of the constituent primary particles is less likely to affect the exterior. Also, the influence from the exterior is less likely to reach the interior. The interaction between the surface composition and the internal composition can produce unexpected effects. An example of an unexpected effect is that when gamma alumina is used as the internal composition, making the surface silica affects the phase transition of the gamma alumina crystal. It is known that gamma alumina undergoes phase transition when heated, but it has been confirmed that gamma alumina present in the constituent primary particles whose surfaces are made of another material does not undergo phase transition even when heated to a temperature at which gamma alumina alone undergoes phase transition. Therefore, the production of the aggregate by dehydration condensation can be carried out at 900°C or higher (preferably 950°C or higher, 1000°C or higher).

[0035] In addition, by using boehmite as the inner composition and silica as the surface composition, the transformation from boehmite to alumina (particularly γ-alumina) due to heating can be suppressed, and therefore the production of the aggregate by dehydration condensation can be carried out at temperatures above 250°C.

[0036] Silica, which is used as the surface composition, is easy to perform various surface treatments, has high physical and chemical stability, and is easy to synthesize. From the viewpoint of improving optical properties, it is preferable to use amorphous silica.

[0037] If the main component is such a constituent primary particle, it is possible to contain primary particles having other compositions (for example, those consisting of a single composition as a whole). Here, "mainly composed" means that it contains 50 mass% or more, preferably 70% or more, and more preferably 90% or more. Examples of particles that can be contained as primary particles other than the constituent primary particles include second particles consisting of oxides of a single composition such as silica and alumina. There are no particular limitations on the particle shape of the constituent primary particles.

[0038] The ratio of the surface to the inside is not particularly limited, but it is preferable that the surface covers the inside with almost no gaps.

[0039] The particulate material of the present embodiment has a modified layer on the surface thereof, the modified layer being made of an organic substance having a double bond. The double bond is preferably introduced as a vinyl group, a methacryl group, an acrylic group, or the like, and more preferably as a methacryl group.

[0040] The modified layer is a layer that covers the surface of the constituent primary particles, and is formed on the surface of the aggregate by surface-treating the aggregate with a surface treatment agent having a double bond. The thickness of the modified layer is not particularly limited, but it is preferable to cover the surface of the particulate material with almost no gaps. The modified layer can be interposed between the aggregated constituent primary particles, or can be coated on the surface of the aggregated constituent primary particles, so that the constituent primary particles are directly aggregated together, and then coated.

[0041] The modified layer is preferably either covalently bonded to the surface of the constituent primary particles or physically bonded by intermolecular force bonds. The organic matter constituting the modified layer is preferably a silane compound condensate formed by surface treatment using a silane compound having a double bond as a surface treatment agent. If the silane compound is a compound having two or more SiOR groups in one molecule, a modified layer made of a condensate can be formed. Commercially available silane compounds having a methacryl group include KBM-502 (3-methacryloxypropylmethyldimethoxysilane), KBM-503 (3-methacryloxypropyltrimethoxysilane), KBE-502 (3-methacryloxypropylmethyldiethoxysilane), KBE-503 (3-methacryloxypropyltriethoxysilane), and KBM-5803 (8-methacryloxyoctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and methacrylsilane: DOWSIL Z-6030 Silane manufactured by Dow-Toray Co., Ltd.

[0042] The method for producing the condensation product of the silane compound can be carried out by using the above-mentioned silane compound as a surface treatment agent and condensing it in a state of contact with the surface of the constituent primary particles (whether before or after forming an aggregate). The constituent primary particles are composed of inorganic materials and usually have OH groups on their surfaces. Therefore, the above-mentioned silane compound can react with the OH groups present on the surface of the constituent primary particles to form a covalent bond.

[0043] Furthermore, when Al2O3 is used as the surface or internal composition of the particulate material of this embodiment, it is preferable that the half-width of the peaks present at 2θ of 45° to 49° and 64° to 67° in X-ray diffraction is 0.5° or more. The peak (first peak) in the 2θ range of 45° to 49° is γ-alumina, and the peak (second peak) in the 2θ range of 64° to 67° is γ-alumina. If the half-width of the peaks present in this range is 0.5° or more, α-alumina is not formed, which is preferable.

[0044] Furthermore, when the particulate material of this embodiment employs boehmite as the surface or internal composition, it is preferable that the half-width of the peaks at 2θ of 37° to 39° and 71° to 73° in X-ray diffraction is 2.5° or less, and / or the half-width of the peaks at 2θ of 45° to 49° and 64° to 67° is 2.5° or less. The peaks in these 2θ ranges are boehmite, and it is preferable that the half-width of the peaks in these ranges is 2.5° or less because boehmite remains.

[0045] (Method of producing transparent resin composition) The method for producing the transparent resin composition of the present embodiment includes a dispersing step, a coating step, an aggregating step, a modifying step, a mixing step, and other steps that are adopted as necessary. The method for producing the transparent resin composition of the present embodiment is a method that can suitably produce the transparent resin composition of the present embodiment described above, and therefore the terms used in the description can be used as they are unless otherwise specified.

[0046] ·Dispersion process The dispersion process is a process in which particles (core particles) having the internal composition are dispersed in a liquid dispersion medium to obtain a dispersion liquid. The core particles can be obtained by a conventional method. For example, they can be produced by reacting a compound that serves as a precursor of the internal composition. For example, when boehmite is used as the internal composition, aluminum hydroxide that has been milled to an appropriate particle size can be used as a precursor, and core particles made of boehmite can be obtained by hydrothermal treatment. Furthermore, aluminum oxide that has been milled to an appropriate particle size can be used as a precursor, and core particles can be obtained by heating it in an acid or alkaline aqueous solution.

[0047] Coating process The coating process is a process in which a precursor, which is a compound that becomes the surface composition by reaction, or colloidal silica is added to the obtained dispersion to generate the surface composition, thereby forming coated particles in which the surface of the core particles is coated with the surface composition. The ratio of the internal composition to the surface composition can be controlled by the amount of precursor added. Any compound may be used as the precursor.

[0048] When silica is used as the surface composition, tetraethoxysilane can be used as a precursor. Tetraethoxysilane easily produces silica in the presence of water. For example, the so-called sol-gel method can be used in which tetraethoxysilane is hydrolyzed in an acidic or basic atmosphere. Colloidal silica adheres to the surface of the core particles and aggregates in the aggregation step described below to form silica as the "surface composition."

[0049] ·Agglomeration process The aggregation step is a step carried out after the coating step, in which the coated particles obtained in the coating step are heated to aggregate. The resulting aggregates can be pulverized or classified to obtain the required particle size distribution. The heating temperature in the aggregation step is a temperature at which dehydration condensation occurs between the coated particles. For example, temperatures over 250°C, 450°C or higher, or 500°C or higher can be exemplified. Heating within this temperature range can improve the strength of the obtained particle material.

[0050] Modification process The modification step is a step carried out after the coating step, and is a step of modifying the surface of the coated particles obtained by the coating step by contacting the surface with a surface treatment agent made of a silane compound having a double bond. The modification step can be carried out either before or after the aggregation step. In other words, the surface treatment can be carried out on the coated particles contained in the aggregate by carrying out the modification step on the aggregate obtained from the coated particles in the aggregation step, or the surface treatment can be carried out on the coated particles before being subjected to the aggregation step, and then the aggregation step can be carried out to form an aggregate from the surface-treated coated particles.

[0051] In the modification step, the method of performing the surface treatment with the surface treatment agent is not particularly limited, but examples include a method in which the surface treatment agent is directly added to the coated particles and mixed by stirring or the like, a method in which the surface treatment agent is dissolved or dispersed in a solvent and then added to the coated particles and mixed by stirring or the like, and a method in which the surface treatment agent is heated and vaporized and then supplied to the coated particles to contact them.

[0052] The amount of the surface treatment agent to be contacted in the modification step is determined so that the refractive index is 1.50 to 1.60. The amount of the surface treatment agent is 2.0 to 6.8 μmol / m based on the surface that communicates with the outside of the aggregate. 2 It is preferable to adopt an amount of 6.0 μmol / m 2 , 5.0 μmol / m 2 , 4.0 μmol / m 2 , 2.67 μmol / m 2 can be independently adopted. It is also preferable to adopt about 15% to 50% based on the mass of the aggregate, and 45%, 40%, 35%, 30%, 25%, and 20% can be independently adopted as the lower and upper limits. Furthermore, the surface treatment agent may be added in its entirety at once, or in its entirety in several portions.

[0053] ·Mixing process The mixing step is a step in which the particulate material as a filler formed through both the aggregation step and the modification step is mixed and dispersed in a transparent resin material as a precursor to form a transparent resin composition. The particulate material used in this step is produced by the steps up to this point. The particulate material becomes a filler either alone or by adding other particulate materials.

[0054] In the mixing step, a curing catalyst can be added at the same time. The obtained transparent resin composition becomes a cured transparent resin composition by curing the contained transparent resin material. It is expected that the double bonds derived from the surface treatment agent introduced on the surface of the particulate material react and bond strongly during curing.

[0055] The method for dispersing the particulate material in the transparent resin material is not particularly limited. For example, the particulate material may be mixed with one of the agents A and B constituting the transparent resin material as a precursor, and then the other agent A and B may be mixed, or the particulate material may be mixed with a mixture of the agents A and B in advance.

[0056] Other processes In addition to the above-mentioned steps, other appropriate steps may be included as necessary. For example, a particle size distribution adjustment step may be adopted. The particle size distribution adjustment step is a step of controlling the particle size distribution of one or more particles selected from the coated particles obtained in the coating step, the core particles to be subjected to the coating step, the aggregates obtained in the aggregating step, and the particle material obtained in the modifying step, by a classification operation, a pulverizing operation, or the like.

[0057] (LED device) The LED device of the present embodiment includes the transparent resin composition of the present embodiment described above that forms an encapsulant, and an LED chip encapsulated with the transparent resin composition. The encapsulant formed by the transparent resin composition serves as an optical path for light generated from the LED chip. EXAMPLES

[0058] The particulate material contained in the filler of the present invention, the method for producing the same, and the transparent resin composition will be described in detail below with reference to examples.

[0059] (Preparation of particle material) - Manufacturing of aggregates consisting of primary particles with silica as the surface composition and boehmite as the internal composition: Dispersion process, Coating process, Aggregation process 40 parts by mass of isopropanol (IPA) was added to 100 parts by mass of Aluminosol 10A (containing 10% by mass of Al2O3; minor axis x major axis is 10 nm x 50 nm; equivalent to core particle) manufactured by Kawaken Fine Chemical Co., Ltd. (dispersion process), and 10 parts by mass of tetraethoxysilane (TEOS; precursor of silica, which is the surface composition) was added. By adopting this mixing ratio, the mass ratio of boehmite to silica in the final particle material obtained is theoretically 78:22.

[0060] After reacting at room temperature for 24 hours (coating step), the mixture was neutralized with aqueous ammonia to obtain a gel-like precipitate consisting of primary particles (aggregation step). The precipitate was washed with pure water, dried at 160°C for 2 hours, and pulverized in a jet mill to an average particle size of 2 μm or less, and then heat-treated at 850°C for 2 hours to obtain the aggregate of this example.

[0061] The resulting aggregates had a volume average particle size of 3.0 μm and a specific surface area of ​​280 m 2 The average particle size was measured using a laser diffraction particle size measuring device. The specific surface area was measured by the BET method using nitrogen.

[0062] Modification process The mass of the produced aggregate (mass of filler) was used as a reference to carry out surface treatment using the following amount of surface treatment agent to form a modified layer to produce the particle material of each test example. As the surface treatment agent, a silane compound having a methacryl group (3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) was used, with the treatment amount set to 15% in Test Example 1-1, 20% in Test Example 1-2, 30% in Test Example 1-3, 40% in Test Example 1-4, and 50% in Test Example 1-5.

[0063] A silane compound having a vinyl group (vinyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., KBM-1003) was used to achieve a treatment amount of 15% (Test Example 1-6). A silane compound having a phenyl group (phenyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., KBM-103) was used to achieve a treatment amount of 30% (Test Example 1-7). A silane compound having an acrylic group (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., KBM-5103) was used to achieve a treatment amount of 30% (Test Example 1-8). These are summarized in Table 1.

[0064] The amount of methacrylsilane used was 15% (2 μmol / m) based on the mass of the aggregate. 2 )~50%(6.67μmol / m 2 The amount of vinylsilane used was 15% (2 μmol / m 2 )~50%(6.67μmol / m 2 ) was examined.

[0065] The particle materials in Test Examples 2-1 to 2-7 were silica particles dispersed into primary particles that had been surface-treated with methacrylsilane, phenylsilane, vinylsilane, and the aforementioned aggregates that had not been surface-treated.

[0066] Test Examples 2-1 to 2-4 are particulate materials that have been surface-treated with methacrylsilane. Test Example 2-1 uses a particle having a volume average particle diameter of 10 nm (manufactured by Admatechs Co., Ltd., YA010C-SM1), Test Example 2-2 uses a particle having a volume average particle diameter of 50 nm (manufactured by Admatechs Co., Ltd., YA050C-SM1), and Test Example 2-3 uses a particle having a volume average particle diameter of 100 nm (manufactured by Admatechs Co., Ltd., YA100C-SM2). Test Example 2-4 uses a particle having a volume average particle diameter of 0.5 μm (manufactured by Admatechs Co., Ltd., SC2500-SMJ).

[0067] Test example 2-5 is a particulate material that has been surface-treated with phenylsilane and has a volume average particle size of 50 nm (YA050C-SP3, manufactured by Admatechs Co., Ltd.). Test example 2-6 is a particulate material that has been surface-treated with vinylsilane and has a volume average particle size of 50 nm (YA050C-SV6, manufactured by Admatechs Co., Ltd.).

[0068] In Test Examples 2-7, aggregates that had not been surface-treated were used as the particle material. These are also summarized in Table 1.

[0069] [Table 1]

[0070] ·Mixing process A transparent resin composition was obtained by mixing 35 parts by mass of the particulate material of each test example with 65 parts by mass of two-liquid silicone (manufactured by Shin-Etsu Chemical Co., Ltd., ASP-1120) using a planetary mixer. For test example 2-7, which was not surface-treated, the particulate material could not be mixed uniformly, so 30 parts by mass of the particulate material was mixed with 70 parts by mass of two-liquid silicone to obtain a transparent resin composition of each test example (mixing step). In addition, in order to obtain a cured product for other evaluations, 25 parts by mass of the particulate material of test example 1-6 was mixed with 75 parts by mass of two-liquid silicone (manufactured by Shin-Etsu Chemical Co., Ltd., ASP-1120) to obtain a transparent resin composition (for other evaluations). These transparent resin compositions were placed in a 5 mm thick mold and heated at 150°C for 4 hours to cure.

[0071] (evaluation) Refractive index and transparency The refractive index was measured for Test Examples 1-1 to 1-7 and 2-1 to 2-4. Test Example 1-1, in which the aggregate was treated with methacrylsilane, had a refractive index of 1.562 (15% treatment amount), Test Example 1-2 had a refractive index of 1.537 (20% treatment amount), Test Example 1-3 had a refractive index of 1.575 (30% treatment amount), Test Example 1-4 had a refractive index of 1.550 (40% treatment amount), and Test Example 1-5 had a refractive index of 1.530 (50% treatment amount). Test Example 1-6, in which the aggregate was treated with vinylsilane, had a refractive index of 1.562 (15% treatment amount). Test Example 1-7, in which the aggregate was treated with phenylsilane, had a refractive index of 1.572 (30% treatment amount).

[0072] The refractive indexes of the particle materials treated with methacrylsilane in Test Examples 2-1 to 2-4, treated with phenylsilane (Test Example 2-5), and treated with vinylsilane (Test Example 2-6) were all 1.45. The results are shown in Table 1.

[0073] The refractive index of the aggregate (Test Example 2-7) was 1.564, and the refractive index of the modified layer formed from methacrylsilane was also about the same, and no consistent tendency was observed with respect to the amount of methacrylsilane used. Although there was a tendency for the material to turn yellow due to methacrylsilane treatment, the effect of coloring could be almost completely eliminated by setting the amount of methacrylsilane used as the mass of the aggregate to 30% or less. The refractive index of the resin material was 1.570.

[0074] Indentation hardness The indentation hardness of the cured product of each test example was measured. The indentation hardness was measured using durometers A and D. The results are shown in Table 1 and Figure 1.

[0075] When the methacrylsilane-treated Test Examples 1-1 to 1-5 and the untreated Test Example 2-7 were examined, as is clear from FIG. 1, the aggregate mass was 15% (2 μmol / m 2 ), the test example 1-1 treated with 50% (6.67 μmol / m 2 ) was found to exhibit a higher indentation hardness than the untreated cured product (Test Example 2-7). In addition, it was found that a smaller treatment amount was preferable between 15% and 50%.

[0076] When comparing the indentation hardness of the methacrylsilane-treated (Test Example 1-3), vinylsilane-treated (Test Example 1-6), phenylsilane-treated (Test Example 1-7), and acrylicsilane-treated (Test Example 1-8), it was found that the cured product treated with methacrylsilane had the highest indentation hardness, followed by the cured product treated with vinylsilane and the cured product treated with acrylicsilane, and then the cured product treated with phenylsilane.

[0077] Other evaluations The total light transmittance (%), linear expansion coefficient (ppm / K), tensile modulus (MPa), cure shrinkage (%), and sulfurization inhibition were evaluated for other cured products for evaluation (samples surface-treated with methacrylsilane as a surface treatment agent in an amount of 35% by mass based on the mass of the filler: prepared in the same manner as in Test Example 1-1) and the control cured product. The results are shown in Table 2. The total light transmittance was measured for a test sample with a thickness of 0.5 mm. The linear expansion coefficient was measured in accordance with JIS K7197-1991. The tensile modulus was measured in accordance with JIS K7161-1:2014. For sulfurization inhibition, a cured product containing silver foil and cured was exposed to air at 40°C and 75% relative humidity for 96 hours, and the silver foil was evaluated as "fair" if it changed from silver to black, and as "excellent" if it did not change color. Weather resistance was evaluated by subjecting sheets molded to a thickness of 0.5 mm to an exposure test equivalent to 3 to 4 months using a Suga Test Instruments Super Xenon Weather Meter. If the ultraviolet-visible transmittance spectrum showed a decrease of 2% or more in the 350 to 650 nm wavelength range from the spectrum before exposure, the test was rated as "fair," and if there was no change of 1% or more, the test was rated as "excellent."

[0078] [Table 2]

[0079] As is clear from Table 2, it was found that the system performed better than the control in all evaluation values ​​examined.

Claims

1. A filler having a particulate material dispersed in a transparent resin material mainly composed of a two-component silicone, The particulate material comprises: an aggregate having a specific surface area diameter based on a surface communicating with the outside of the material of 0.8 nm to 80 nm, which is composed of primary particles made of inorganic substances having different surface and internal compositions, and in which the particles are bonded and fused together by dehydration condensation; A modified layer made of an organic material that is bonded to and covers the surface of the primary particles by covalent bonding or intermolecular bonding, The volume average particle size of the aggregates is greater than 0.1 μm; the surface composition has a refractive index different from that of the interior composition; an abundance ratio between the composition on the surface and the composition in the interior is such that a transmittance (at a wavelength of 400 nm) of a cured product having a thickness of 2 mm obtained by dispersing 10 parts by mass of the aggregate in 100 parts by mass of the transparent resin material and curing the aggregate is 80% or more; the primary particles each have an interior composed of at least one of boehmite and γ-alumina and a surface composed of silica; the modified layer is formed by surface-treating the particulate material with a surface treatment agent having a double bond so that the refractive index of the particulate material is 1.50 to 1.60; The particulate material has a volume average particle size of 0.2 μm to 5.0 μm; the surface treatment agent is a silane compound, and is applied to the surface of the aggregate in an amount of 2.0 to 6.8 μmol / m 2 based on the surface that communicates with the outside of the aggregate; The surface treatment agent has a methacryl group, The organic substance is a condensation product of a silane compound. Filler.

2. The filler according to claim 1, wherein the surface treatment agent is applied to the surface of the aggregate that is in communication with the outside in an amount of 2.0 to 5.33 μmol / m 2 .

3. The filler according to claim 1 or 2, and the transparent resin material in which the filler is dispersed; A transparent resin composition for electronic devices comprising:

4. The transparent resin composition according to claim 3 , wherein the electronic device is an LED.

5. A method for producing the filler according to claim 1 or 2, comprising the steps of: a dispersing step of dispersing core particles having the internal composition in a liquid dispersion medium to obtain a dispersion; a coating step of dissolving a precursor of the surface composition in the dispersion liquid, and then converting the precursor into the surface composition to coat the core particles to form coated particles; an aggregating step of heating the coated particles to cause dehydration condensation to bond and fuse the particles together to form aggregates; The coated particles are made of an organic substance that is surface-treated with a surface treatment agent having a double bond so that the refractive index is 1.50 to 1.60, and the surface of the coated particles is coated with the organic substance. a modification step of forming a modified layer bonded by covalent bonds or intermolecular forces; having the surface treatment agent is a silane compound, and is applied to the surface of the aggregate in an amount of 2.0 to 6.8 μmol / m 2 based on the surface that communicates with the outside of the aggregate; The surface treatment agent has a methacryl group. A method for producing a filler.

6. A step of producing the filler by the filler production method according to claim 5; a mixing step of mixing the particulate material obtained in the step of producing the filler with the transparent resin material which is a precursor to form a transparent resin composition; A method for producing a transparent resin composition for electronic devices comprising the steps of:

7. The transparent resin composition according to claim 4, An LED chip encapsulated with the transparent resin composition; An LED device having the following structure:

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